Dehydration of liquefied petroleum gas



March 16, 1954 M. R. MoRRow DEHYDRATION OF' LIQUEFED PETROLEUM GAS Filed oct. 26, 195o' IN V EN TOR.

/orr/j narrow? Patented Mar.` 16, 1954 Morris" lvlr'orriwvgl Baytown,n Tx. assigning, by

mesne assignments; to St'arniaril7 Oil' D'evelonment Company, Elizabeth; N. J., av corporation' of'Delawaref Application October26, 1950,. Serial- No.v 192,280;

Tire presenti invention is d'iriantenk to aY method fory dehydrating Iiqneiied. normally' gaseous? hy*- drocarbons More particularly-- the invention. is directedA to the.l removal of WaterA as suchv or" as ydirates from liquefied: normally gaseous hydroe carbons having n'o more than'. four: carbon` atoms the` molecule; More particularly, thefinvention has to do with the production'ofsubstarrtially dehydrated propane and butane for sale asy a liqnefiedipetroleum gas.

application is a continuation-impart oi Serial- No'. 2210231 filed April; 19 i948, now' abancloned', the name of Morris R. Morrow and en"- titled:Production of Eehydratedfliioueed Petro- Ieunr cias."l

In recenti years there has built" up4 a: large 'x'narl'etA` for* liqueedl petroleum gases; This marletfhas been filled" by tlienatural gasoline indizstryf' from"y its supplies of propane' and butane; It has been: the-practice to' litiuei'y these normally gaseous" hydrocarbons and pla-ce the Iman-ferialy on 'sale for' domestic and' yindustrial purposes. In niarl'tetingthese Iique'eci gases; it is' important thatsubstantially7 all Water either as suoli or in tieeformor hydrates be removed from the liqueffied gases: if the water is notVL removed, there is considerable danger of line and storage vessel plugging. by the'n formatie'n or hydrates and ice during the employment of these gases as fuels.V

Tlne ind'stryf has' taken cognizance" of the' reqoirements for a substantially deliydiatedA rel and has employed the conventional denydrating media removing' water andr preventing hy'- di'atei formation. Fory example, gasesA and' liqueg'ases have been: contacted hygroseopic materiali which removed water vapors. Calcium chloride brine; andA die'thylene glycol have been used in removing Water from lique'ed petroleum gases. Adsorption: media suon asf silica gel and other solids that lia-ve an ainity forwater4 have afsobeerr used removing water from lquened petroleum gases'.

It willV be that thefbregoing prior art methods; require special equipment and chemii eels for iernoving Waterv from the normally gase-l ons material before it is suitable for use as a fuel.

It therefore, obiecto the present involitionA to provide a simple" andi economical proce'ssfor' removing" water from? normally gaseous hydrocarbons by aprocessl involving distillation and' flashing'.

.iiiotherobiect of' the present invention is to :nov-idea; substantially dehydrated propanewhich is suitable forus'e as a fuel. I

.Af timber object or the present invention is to. provide. a. process A` in which: a.v watenfcnnf taini'ng hydrocarbon having; no` more thanv four carbon. atoms is. subjected', to. aA sequence or' dis,- t'illing. and' flashing, steps, to remove substantially all water therefrom.,

The objects of the present. invention may, be achieved by subjectingrv a` Water-Wet. hydrocarbon having three to four. carbon atoms inthemolecule to distillation, following, which the condensed overhead fractionhas water removed from it, and is then subjected to a dashing@ operation. to. re move further quantities. of Water therefrom.

Briefly then the invention beY described as involving forming.` a stream of a, Water-oontaining hydrocarbon fraction suchs as propane; or butano, subjecting the water-containing'. stream to distillation to form anoverhead; fractibn. in.- oluding substantially all" the Water contained in the feed stream. and condensing. the overhead Jfraction. toiorm a hydrocarbon phase, and` awater phase. The Water: phase is separated from the hydrocarbon phase and is; removedv from the system. While the hydrocarbonrphase is thensubfjecte'd to a simple hashingV operation toremove additional quantities of' water. The remaining liquidi hydrocarbon phase is substantiallydenydrated andi is suitable for use as a fuel for domestic' and' industrialuses.

The hydrocarbons: employed'.4 in the present, in.- vention. ordinarily willA be propane, isobntane.,y and normal butane. The' invention has greatest ap,- plic'ation to the parafni'o hydrocarbnnshaving three to four' carbon atoms in the molecule', but it.' also' has application to. removal ofi water from the olenicjhydrocarbons: having three to tour carbon; atoms in the molecule. For example, the butylenes, propylene', and butadiene are, impor'- tant feed stocks to catalytic conversion. operations. such as alkyl'ati'on and polymerization, In some of the. catalytic conversion operations it ist very important that substantially all. water be removed from the feed stocks'. The present invention thereforeY has application to theV removal of water from suclr hydrocarbons The temperatures employed in the dashing operation of the present invention range from about 20 F. to aboutv 160 F. with temperatures from about 40 to about 7'0" F; being apreferred' range. Good results may be obtained by hashing the Wet hydrocarbon at a temperature in the' range between about to '10 F.

The-invention will now be further illustrated by' reference to the drawing in which thesingle lgure represents a flow) diagram showing a preferred mode thereof.

Referring n'ovva to' the drawing, numeral' H designates a feed line through which a stream including, for example, propane containing a substantial amount of water is introduced into the system from a source not shown. The wet propane discharges into line I2 which in turn conducts the Wet propane into a distillation Zone I3 which is illustrated as a single distillation tower. Distillation zone I3 will be understood to include suitable internal baiting equipment such as bubble cap trays and other contacting devices to insure intimate contact between vapors and liquids. In distillation zone I3 temperature and pressure conditions are adjusted by a heating means illustrated by heating coil I4 to obtain as an overhead fraction by line I5 a fraction including substantially propane and the water charged with the wet propane stream. The conditions employed in distillation zone I3 will vary depending on the hydrocarbon composition of the feed stock. If it is assumed that distillation Zone I3 is a distillation tower including about 30 plates and the feed mixture includes normal butane, isobutane, and propane, the propane would be removed as an overhead product and the normal butane and isobutane mixture as a bottoms product. Under these conditions, with cooling water at a temperature of about 80 F. it would be possible to operate zone I3 with a top temperature of about 90 F. and at a pressure of about 164 pounds per square inch gauge. The bottom temperature will be somewhat higher and should be sufficient to drive all the propane out of the mixture of isobutane and normal butane.

There are removed from the bottom of distillation zone I3 by line I6 controlled by valve I'I any higher boiling hydrocarbons such as iso and normal butane and the like which may have been included in the feed stream introduced by line I I.

The overhead fraction withdrawn by line I5 passes through a condenser I 8 and thence into a drum I9 which is of suicient capacity to allow a residence time for the formation of a liquid hydrocarbon phase and a water phase. The water is separated and withdrawn from drum I9 by line 20 controlled by valve 2I while the hydiverted by line 24 to the top of distillation vzone I3 to provide reflux therein. Drum 23 is similar to drum I9 and is of sufcient capacity to provide a residence time for a separation of any water contained in the stream introduced thereto by line 22. Anywater that may separate in drum 23 may be withdrawn therefrom by line 25 controlled by valve 26.

. The hydrocarbon, having removed therefrom substantially all water which is separable by gravity, is discharged from drum 23 by line 2 into either of drums 28 or 29. Assuming for the moment that valve 30 in line 3I is closed-and valve 32 in line 21 is open, the propane is routed by line 21 into drum 29 until drum 29 contains a substantial amount of propane. After drum 2-9 has been lled to the point desired, valve 32 is closed and valve 30 in line 3| is opened and the propane is then routed to drum 28. Assuming that propane is being routed to drum 28 and drum 29 has been filled to the desired level with propane, valve 33 in line 34 connecting into line I2 is opened allowing a simnle flashing operation to take place in drum 29. By reducing the pressure in drum 29, a liquid phase and a gas phase is formed therein. As a result, any water which is contained in the'propane indicated by the shaded portion 35 is flashed into the portion of the vessel indicated by the numeral 36. This gas phase contains substantially a greater quantity of Water than the liquid phase 35 and is bled into line I2 and may be discharged thereby along with the feed propane stream to distillation zone I3 as has been described. After the iiashing operation has been concluded, valve 33 may be closed and a substantially dry propane withdrawn from vessel 2S by line 37 controlled by valve 33.

When drum 29 has been emptied propane may again 'be routed thereto by opening valve 32 in line 27. The propane in drum 28 may then be caused to undergo the flashing operation by opening valve 39 in line I2. After the flashing operation has been concluded, substantially dry propane may be withdrawn from drum 2&3 by line 40 controlled by valve'4I.

Under some conditions it may be undesirable to charge to distillation zone I3 the propane containing water flashed from the prop-ane in drums 28 and 29. Under these circumstances, valve 42 in line I2 is closed and valve 43 in line 44 is opened to allow the bleed wet propane stream to be discharged from the system for further use as may be desired.

It will be seen from the foregoing description taken with the drawing that a simple and effective process is provided whereby a feed hydrocarbon stream is subjected to a sequence of operations including distilling, condensing,A and flashing to remove substantially all water therefrom.

The invention will be further illustrated by reference to the following example. A wet feed stream containing propane and water was charged to a distillation tower to obtain .an overhead fraction including propane and substantially all the water contained in the feed stream. This stream was cooled and condensed and water separated therefrom. Twenty thousand volumes of .the liquid propane stream from which water had been separated was then submitted to a flashing operation at a temperature of between 60 and '70 F. to remove 750 parts of propane and Water. The propane subjected to the flashing operation contained about 40 parts per million of water and failed to pass lthe cobaltbromide test. After the flashing. operation, the liquid propane contained less than 23 parts per million of waterv and passed the cobalt-bromide test. A description of the cobalt-bromide test may be found in the Technical Standardsof the Natural Gasoline Association of America and a description of the test method may be found in the Tentative N G. A. A. Standard 2140, Revised July 1940, page 4.

This propane which had beenl treated in accordance with the present invention was then suitable for use as a domestic or industrial fuel.

In another example a hydrocarbon fraction containing propylene. and propane with small amounts of ethylene and butanes was produced in a commercial distillation unit in an amount in excess of 2400 barrels per day. This fraction contained on an average of 15% of propylene and propane, the remainder being ethylene and butanes. Actually the propylene content varied from about 5% to 30% by volume of the mixture. The propane-propylene fraction was then cooled in horizontal cylindrical drums until a total of 2552 barrels of the propane-propylene fraction was obtained. A sample representing the propane-plpylene fraction was tested for water content which was vfound to be .20 parts per mjL lion of dissofyd Followirigthis analysis, the ,drums Wlfliclgl-V were provided with piping coniiccti'ons and valves to permitflashing vapor from the top ofthe drums were opened-topermit fiashing of thev contents thereof overa period. of 2y hours; 1760 barrels'- of the propane-propylene fraction as liquid was evaporated and. removed from the drums as vapor-f. thel operation after hour of the 'ashi'ng operation theliquid propane-propylene fraction in the drums was sampled for water content. The analysis showed the propane-propylene fraction to contain below 10 parts per million of Water.

As another example of the present invention, approximately 450 gallons of a butane fraction containing about 80 parts per million of dissolved water were charged to a still consisting of a horizontal drum surmounted by a fractionating column equivalent to approximately 10 theoretical trays at total reflux. This still Was operated at an elevated pressure of about 75 pounds. Heat Was applied to the still and vapor passed from the drum into the column and to a condenser connected to the column. The overhead was totally condensed. The condensate from the condenser was passed to a settler Where the overhead was separated into liquid butane and water. The liquid butane was returned to the top of the column While the Water remained in the settler or separator. The process of distillation was allowed to continue for a period of 4 to 5 hours until the Water level in the settler remained approximately constant. Approximately 70 cubic centimeters of water were then withdrawn from the settler and discarded. The heating was discontinued and after the butane had been allowed to cool it was tested for Water content and found to contain less than l0 parts per million of Water.

In a still further example a butadiene stream of approximately 98% by volume of ybutadiene having a water content in the liquid state of 500 parts per million Was evaporated to remove 80% by volume of the liquid butadiene. Analysis of the remaining liqueed butadiene showed it contained 184 parts per million of Water.

A mixture of normal butylene and butane in the approximate ratio of 75% to 25% which contained 319 parts per million of water was vaporizcd to the extent of 80 volume per cent. The remaining 20 volume per cent of the butylenebutane fraction was analyzed and found to contain 82 parts per million of Water.

The Water content of the fractions including the propylene-propane fraction, the butadiene fraction and the butylene-butene fraction were 'a determined by a modified Karl Fischer procedure l(Angew. Chem. 48, 39441935).

It will be seen from the several examples that by proceeding in accordance with the present invention including a distillation operation and a flashing operation that it is possible to reduce to a marked extent the Water content of a liquefied petroleum fraction having from 3 to 4 carbon atoms in the molecule.

The nature and objects of the present invention having been fully described and illustrated, what I Wish to claim as new and useful and to secure by Letters Patent is:

1. A method for dehydrating a Water-containing normally gaseous hydrocarbon feed having from three to four carbon atoms in the molecule which comprises rectifying said water-containing normally gaseous feed hydrocarbon to obtain an overhead fraction including hydrocarbon and substantially al1 the water in said feed and a bottoms fraction-l substantiellyfv freeof water, condensingf said overhead fraction and separating Water therefrom, dashing said, condensed over,- head fraction to form a gaseous phase and` a liquid. phase, and recovering4 from said` liquid phasev a: substantially dehydrated hydrocarbon.

2. A method in accordance with claim 1 in which the normally gaseous' feed hydrocarbon is propane? '3.- A. method in accordance with claimt 1i in Which the normally gaseous feed hydrocarbon is butane.

4. A method for removing Water from a watercontaining normally gaseous feed hydrocarbon having from three to four carbon atoms in the molecule Which comprises forming a feed stream of said normally gaseous feed hydrocarbon, rectifying said stream under conditions to obtain an overhead fraction including substantially all the Water in said feed hydrocarbon and a bottoms fraction substantially free of Water, condensing said overhead stream to form a hydrocarbon phase and a water phase, separating said Water phase from said hydrocarbon phase, hashing said hydrocarbon phase to form a gaseous phase and a liquid phase, admixing said gaseous phase with water-containing feed hydrocarbon, and recovering from said liquid phase a substantially dehydrated hydrocarbon.

5. A method in accordance with claim 4 in Which the normally gaseous feed hydrocarbon is propane.

6. A method in accordance with claim 4 in which the normally gaseous feed hydrocarbon is butane.

7. A method for dehydrating a water-containing propane stream Which comprises feeding said propane stream to a rectification zone, rectifying said propane toY obtain an overhead fraction including propane and substantially vall the Water in said feed propane and a bottoms fraction substantially free of Water, condensing said overhead fraction and separating Water therefrom, flashing said condensed overhead fraction to form a gaseous phase and a liquid phase, admixing said gaseous phase with said feed propane, and recovering from said liquid phase substantially dehydrated propane.

8. A method in accordance with claim 7 in which the Water-containing propane stream is a mixture of propane and propylene.

9. A method for dehydrating a water-containing mixture of propane and butane which cornprises feeding said mixture to a rectification zone, rectifying the mixture to obtain an overhead fraction including propane and butane and substantially all the water in the feed mixture and a bottoms fraction substantially free of Water, condensing said overhead fraction and separating Water therefrom, flashing said condensed overhead fraction to form a'gaseous phase and a liquid phase, admixing said gaseous phase with said feed mixture and recovering from said liquid phase substantially dehydrated propane and butane.

MORRIS R. MORROW.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 1,556,710 Rudigier Jan. 1'7, 1928 2,067,349 Schuftan Jan. 12, 1937 (Uther references on following page) Number Number 7 UNITED STATES PATENTS Name Date Gerlach Dec. 17, 1940 Walker Apr. 7, 1942 Keith June so, 1942 5 Shipley Jan. 30, 1945 FOREIGN PATENTS Country Date Great Britain Oct. 25, 1950 le) OTHER REFERENCES Phase Equilibrium in Hydrocarbon Systems, by Reamer et a1., Ind. and Eng. Chem., vol. 36 (1944), pp. 381-383.

Water Content of Propane, by Poettman et. al., Petroleum Rener, December 1946, vol. 25, No. 12, pp. 125-128.

Ice and Refrigeration, June 1948, page 50, Figure 1. 

1. A METHOD FOR DEHYDRATING A WATER-CONTAINING NORMALLY GASEOUS HYDROCARBON FEED HAVING FROM THREE TO FOUR CARBON ATOMS IN THE MOLECULE WHICH COMPRISES RECTIFYING SAID WATER-CONTAINING NORMALLY GASESOUS FEED HYDROCARBON TO OBTAIN AN OVERHEAD FRACTION INCLUDING HYDROCARBON AND SUBSTANTIALLY ALL THE WATER IN SAID FEED AND A BOTTOMS FRACTION SUBSTANTIALLY FREE OF WATER, CONDENSING SAID OVERHEAD FRACTION AND SEPARATING WATER THEREFROM, FLASHING SAID CONDENSED OVERHEAD FRACTION TO FORM A GASEOUS PHASE AND A LIQUID PHASE, AND RECOVERING FROM SAID LIQUID PHASE A SUBSTANTIALLY DEHYDRATED HYDROCARBON. 